多级孔道ZSM-5分子筛的制备及其催化裂解性能

石油炼制与化工 ›› 2016, Vol. 47 ›› Issue (4): 65-70.

多级孔道ZSM-5分子筛的制备及其催化裂解性能

张伟¹,王峰¹,雍晓静¹,巩雁军²

1. 神华宁夏煤业集团煤炭化学分公司
2. 中国石油大学CNPC催化重点实验室

收稿日期:2015-09-09 修回日期:2015-11-10 出版日期:2016-04-12 发布日期:2016-04-19
通讯作者: 张伟 E-mail:zhwei20031002@126.com
基金资助:
宁夏回族自治区科技支撑计划资助；神华集团科技创新项目

PREPARATION OF HIERARCHICAL POROUS ZSM-5 ZEOLITE AND ITS CATALYTIC CRACKING PERFORMANCE

Received:2015-09-09 Revised:2015-11-10 Online:2016-04-12 Published:2016-04-19

摘要/Abstract

摘要：

通过直接合成或后改性等方法制备了具有多级孔道结构的ZSM-5分子筛样品，用X-射线衍射(XRD)、扫描电镜(SEM)、N2吸附-脱附、程序升温氨脱附(NH3-TPD)方法对其进行了表征，并在固定床反应器中对其催化裂解性能进行了评价。结果表明：与常规ZSM-5分子筛相比，多级孔道结构的ZSM-5分子筛具有比表面积高、介孔孔体积大、介微孔比率高等优势。在分子筛内引入多级孔道，在正己烷催化裂解反应中目的产物丙烯更易扩散，氢转移反应得到有效抑制，可提高丙烯收率。具有最高介微孔比率的纳米薄层NZSM-5-300样品上，其乙烯选择性为15.8%，丙烯选择性为40.1%，双烯总选择性为55.9%。通过对比发现：介微孔比率高的催化剂，正己烷转化率下降速度减缓，寿命延长。

关键词: 多级孔道分子筛, ZSM-5, 介微孔比率, 催化裂解, 丙烯选择性

Abstract:

Hierarchical porous ZSM-5 zolites were prepared by direct synthesis and post modification and characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption/desorption and temperture-programmed desorption of ammonia (NH3-TPD), respectively. The catalytic cracking performance of the samples was evaluated in a micro fixed-bed reactor. The results indicate that compared with conventional ZSM-5, the hierarchical porous ZSM-5 zeolites have the advantages in higher surface area, mesoporous volume and ratio of meso/micro. The propylene yield is increased because the mesopores are introduced in the modified sieve, which make the product more easily to diffuse and th effectively suppress the hydrogen transfer reaction. Over the nanolayered NZSM-5-300 with the highest ratio of meso/micro, the selectivity of ethylene and reaches 15.8% and 40.1%,respectively. The test results indicate that with increase of meso/micro ratio, the sample exhibits better stability and lower deactivation rate as well as longer.

Key words: hierarchical porous zeolite, ZSM-5, meso/micro ratio, catalytic cracking, propylene selectivity

张伟王峰雍晓静巩雁军. 多级孔道ZSM-5分子筛的制备及其催化裂解性能[J]. 石油炼制与化工, 2016, 47(4): 65-70.

参考文献

[1] 王松汉, 何细藕. 乙烯工艺与技术[M]. 北京: 中国石化出版社, 2000. [2] 徐强, 陈丙珍, 何小荣, 等. 石脑油在SRT-IV型工业炉清洁辐射管中裂解的数学模拟[J]. 计算机与应用化学, 2001, 18(3): 223-228. [3] Dancuart L P, Mayer J F, Tallman M J, et al. Performance of the Sasol SPD naphtha as steam cracking feedstock[J]. American Chemical Society, Division of Petroleum Chemistry. 2003, 48(2): 132-138. [4] 何海军, 韩金兰, 等. Lurgi MTP工艺的技术经济分析[J]. 煤质技术，2006，3: 45-47. [5] Liebner W, Rothaemel M. Greating value from standard natural gas[J]. Petrochemicals and Gas Processing. 2003 : 141-147. [6] Koempal H, Liebner W. Lurgi’s Methanol To Propylene (MTP ) Report on a successful commercialisation[C]. Studies in Surface Science and Catalysis 2009, 167: 261-267 [7] Keading W W, Butter S A. Production of chemicals from methanol: I. Low molecular weight olefins[J]. Journal of Catalysis, 1980, 61, 155-164. [8] Dehertog W J H, Froment G F. Production of light alkenes from methanol on ZSM-5 catalysts[J]. Applied Catalysis A: General 1991, 71, 153-165. [9] Perez-Ramirez J, Christensen C H, Egeblad K, et al. Hierarchical zeolites: Enhanced utilisation of microporous crystals in catalysis by advances in materials design[J]. Chemical Society Reviews, 2008, 37(11): 2530-2542． [10] Moiler K, Bein T. Mesoporosity-a new dimension for zeolites [J]. Chemical Society Reviews. 2013, 42(9): 3689-3707． [11] Christensen C H, Johannsen K, Schmidt L, et al. Catalytic benzene alkylation over mesoporous zeolite single crystals：Improving activity and selectivity with a new family of porous materials[J]. Journal of the American Chemical Society. 2003, 15(44): 13370-13371． [12] Serrano D P, Aguado J, Escola J M, et al. Hierarchical zeolites with enhanced textural and catalytic properties synthesized from organofunetionalized seeds[J]. Chemistry of Materials. 2006, 18(10): 2462-2464． [13] Perez-Ramirez J, Verboekend D, Bonilla A, et al. Zeolite catalysts with tunable hierarchy factor by pore-growth moderators[J]．Advanced Functional Materials 2009，19(24)：3972-3979．

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